Ferroelectrics Letters Section

ISSN: 0731-5171 (Print) 1563-5228 (Online) Journal homepage: http://www.tandfonline.com/loi/gfel20

Well-dispersed Nd:Y2O3 nanopowders fabricated

by a modified solution-combustion method

Xiaorong Zhang, Guifen Fan, Xiaohong Wang, Ming Fu & Wenzhong Lu

To cite this article: Xiaorong Zhang, Guifen Fan, Xiaohong Wang, Ming Fu & Wenzhong Lu
(2016) Well-dispersed Nd:Y2O3 nanopowders fabricated by a modified solution-combustion
method, Ferroelectrics Letters Section, 43:1-3, 19-24, DOI: 10.1080/07315171.2016.1174507

To link to this article: http://dx.doi.org/10.1080/07315171.2016.1174507

Published online: 26 May 2016.

Submit your article to this journal

Article views: 4

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=gfel20

Download by: [University of California, San Diego] Date: 21 June 2016, At: 13:59
 FERROELECTRICS LETTERS SECTION
, VOL. , –
http://dx.doi.org/./..

Well-dispersed Nd:Y O nanopowders fabricated by a modified

solution-combustion method
Xiaorong Zhanga,b , Guifen Fana,b , Xiaohong Wanga,b , Ming Fua,b , and Wenzhong Lua,b
a
School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan,
PR China; b Key Lab of Functional Materials for Electronic Information, MOE, Huazhong University of Science and
Technology, Wuhan, PR China
Downloaded by [University of California, San Diego] at 13:59 21 June 2016

ABSTRACT ARTICLE HISTORY

Ammonium polyacrylate was adopted for the first time to fabricate Accepted  October 
nanosized Nd:Y2 O3 powders with good dispersity through solution-
KEYWORDS
combustion method. Results indicate that cubic Y2 O3 can be synthe-
Nd:Y O nanopowders;
sized at a relatively low temperature (300°C) and that the crystallinity of solution calcination method;
powder increases with increased calcination temperature. TEM obser- ammonium polyacrylate;
vations reveal that the influence of improve with increased organic-fuel dispersity; microstructure
dosage. Well-dispersed Nd:Y2 O3 particles with a narrow size distribu-
tion of 20–40 nm can be obtained when the mass ratio of ammonium
polyacrylate to yttrium nitrate is 0.5:1. Therefore, ammonium polyacry-
late is a new fuel that can be used to prepare well-dispersed Nd:Y2 O3
nanopowders.

1. Introduction
Current interest in yttria (Y2 O3 ) originates from its remarkable physical and chemical proper-
ties, such as high-temperature stability, high corrosion resistance, and superior optical trans-
parency. These outstanding properties make Y2 O3 a promising material to use for manufac-
turing microwave with magnetic material and weapons and optical materials as transparent
ceramics, laser host material, phosphor and so on. In addition, many applications of Y2 O3
ceramics require doping with luminescent ions, and Nd3+ ion is the most popular ion for laser
application[1–4]. The quality of powders is crucial for fabricating high-performance ceram-
ics. The powders must have high purity, fine grain size, narrow size distribution, and good
dispersity[5, 6]. However, nanoscale particles tend to agglomerate because of their larger sur-
face areas, which adversely affects sinterability of the powder and properties of the ceramics
[7, 8]. Therefore, simple and feasible synthesis routes must be explored to obtain high quality
powders with fine grain size and good dispersity for fabricating high-performance Nd:Y2 O3
ceramics. To date, numerous powder preparation methods have been reported for Nd:Y2 O3 ,
such as co-precipitation[1], hydrothermal[9, 10], ball milling[8], sol–gel[6, 11], and combus-
tion[12, 13] techniques. Among them, combustion has the advantages of simple experimen-
tal procedure, relatively low reaction temperature, and short reaction time. Powders obtained

CONTACT Wenzhong Lu lwz@mail.hust.edu.cn

Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gfel.
Communicated by Dr. George W. Taylor
©  Taylor & Francis Group, LLC
 20 X. ZHANG ET AL.

by this method also have fine grain size, narrow size distribution, and homogeneously doped
Nd3+ ion. In combustion method, the precursor undergoes dehydration and combustion for a
short period of time without an external heat source, producing a large amount of gas and heat
from the exothermic reaction between the metal nitrates and fuel, resulting in well-dispersed
powders[14, 15]. Hence, the combustion method is very suitable for preparing Nd:Y2 O3 pow-
ders. In addition, a suitable organic fuel, an important integrant of the precursor, is needed
adjust the dispersity of the product. Currently, some of the main organic fuels are widely
adopted include citric acid (C6 H8 O7 )[12], urea (CH4 N2 O), carbohydrazide (CH6 N4 O)[15],
glycine (C2 H5 NO2 )[13], and sucrose (C12 H22 O11 )[16].
In fact, ammonium polyacrylate (NH4 -PAA) has great potential to be a superior organic
fuel because NH4 -PAA easily dissolves in water, resulting in molecular chains that make up
the adsorption layer at the particle surface. In this study, NH4 -PAA was firstly employed to
synthesize nanosized Nd:Y2 O3 powders using the solution-combustion method. The synthe-
Downloaded by [University of California, San Diego] at 13:59 21 June 2016

sis process of the powders, as well as the effects of organic-fuel dosage and calcination tem-
perature on the characteristics of the powders, was studied in detail.

2. Materials and methods

Yttrium nitrate [Y(NO3 )3 ·6 H2 O; 99.9%; Aladdin, YN for short], neodymium nitrate
[Nd(NO3 )3 ·6 H2 O; 99.9%; Aladdin], and Ammonium polyacrylate (MW ࣈ1000∼3000) were
used as starting materials. Predetermined amounts of all metal precursors were weighed
according to the stoichiometric formula Ndx Y2−x O3 (x = 0, 0.04, 0.1). Stock solutions of
salts and fuel were dissolved in distilled water and mixed well. NH4 -PAA easily dissolves in
water, enabling molecular chains to fully develop. Consequently, thicker adsorption layers
were obtained on the particle surface. The total fuel to metal nitrate mass ratios were set at
0.2:1 and 0.5:1. The dry gel was then heated at 300, 400, 500, 600, and 800°C for 2 h.
Thermogravimetric analysis (TG-DSC) of the reaction process of the precursor was per-
formed using a simultaneous thermal analyser (STA 449 F3 Jupiter, Germany) by heating the
precursor to 900°C at a heating rate of 10°C/min in air. Phase and crystal structure analyses of
the powders obtained under different conditions were carried out by X-ray diffraction (XRD;
Rigaku Dmax-rC, Japan) using Cu Kα radiation and Fourier transform infrared spectroscopy
(FT-IR; Bruker, model Vector 22, Germany) using KBr pellets. Microstructures of the pow-
ders were investigated with transmission electron microscopy (TEM; JOEL JEM-2100, 200 kV,
Tokyo, Japan).

3. Results and discussion

Typical TG-DSC curves for dry gel with NH4 -PAA:YN = 0.5:1 are shown in Fig. 1. The gel was
prepared by drying the mother liquor at 80°C for 24 h. A small endothermic peak with 7.7%
weight loss was found in the TG-DSC curves, which is mainly attributed to evaporation of
water in the mother liquor. With increased temperature from 200°C to 300°C, an exothermic
peak in DSC curve, corresponding to strong weight loss in TG curve was detected, illustrat-
ing the dehydration of absorbed water and decomposition of residual organic and nitrates[12].
With continuously increased temperature, no weight change was found, whereas heat signals
were observed in the TG-DSC curves. All heat signals, as well as the ∼74.2% total weight loss,
were achieved below 400°C, indicating that the decomposition of the precursor and crystalli-
sation of the powders were finished before 400°C.
 FERROELECTRICS LETTERS SECTION 21
Downloaded by [University of California, San Diego] at 13:59 21 June 2016

Figure . TG-DSC curves for the precursors of Y O (NH -PAA:YN = .:).

The XRD patterns of Y2 O3 and Nd:Y2 O3 obtained by calcining the mother liquor at dif-
ferent temperatures for 2 h are shown in Fig. 2. The primary crystal phases of Y2 O3 were
formed at 300°C according to the JCPDS card of cubic Y2 O3 (No. 86–1326) (Fig. 2(a)). How-
ever, the diffraction peaks are weak and broad, indicating poor crystallisation of the powders
because of the low calcination temperature. In addition, some black spots were found in the
powders because the organic fuel has still not completed decomposition. With increased cal-
cination temperature, the degree of crystallinity of the Y2 O3 powders increase and black spots
in the powders disappear. The Y2 O3 powders obtained at 400°C and higher temperature show
pure phase of Y2 O3 with good crystallinity. XRD results are consistent with TG-DSC curve
results.

Figure . XRD patterns of Y O and Nd:Y O powders obtained at different calcination temperatures with
NH -PAA:YN = .:. (a) Y O /°C; (b) Y O /°C; (c) Y O /°C; (d) Y O /°C; (e) Nd. Y. O /°C;
(f) Nd. Y. O /°C.
 22 X. ZHANG ET AL.
Downloaded by [University of California, San Diego] at 13:59 21 June 2016

Figure . FT-IR spectra of Y O samples obtained with NH -PAA:YN = .:. (a) °C; (b) °C.

An amplified XRD pattern in the range of 2θ = 27.5–31.0 is shown as an inset in Fig. 2. The
diffraction peaks of the Nd:Y2 O3 powders shift to a low angle compared with that of pure Y2 O3
powders. With increased doping amount, the deviation of the angle increased because of the
larger atomic radius of Nd3+ replacing the smaller atomic radius of Y3+ in crystal cells, leading
to a larger lattice constant. However, the diffraction characteristics of Y2 O3 crystalline phases
were still observed in the XRD patters. The results clearly show that Nd3+ can successfully
dope into the lattice of Y2 O3 .
The FT-IR spectra of Y2 O3 samples obtained at different temperatures with NH4 -PAA:
YN = 0.5:1 are shown in Fig. 3. As shown in Figs. 3(a), the peaks observed at 545, 456, and
411 cm−1 are consistent with Y–O lattice vibration[12, 17], indicating that crystalline Y2 O3
was formed. However, in Fig. 3(a), the OH− stretching vibration peak at about 3400 cm−1 , the
C–H stretch band at around 2900 cm−1 , and the vibrations of CO3 2− at around 840, 1100, and
1519 cm−1 are also observed[1,18]. The absorption band around 1400 cm−1 is the character-
istic vibration peak of NO3 − . The residuals cannot be eliminated completely at 300°C. The
analysis results show that a higher calcination temperature is necessary in preparing Y2 O3
powders, although the Y2 O3 phase can be formed at only 300°C.
Compared with Fig. 3(a), in Fig. 3(b), some absorption peaks corresponding to residual
organic compounds become weaker, whereas other peaks of residual organic compounds
completely disappear, indicating that the residual organic compounds of the precursor reduce
with increased calcination temperature; however, the residuals cannot be eliminated com-
pletely at the synthesis temperature range.
TEM images of Nd:Y2 O3 powders fabricated under different reaction conditions are shown
in Figs. 4(a)–(d). The organic fuel content and calcination temperature exert obvious effects
on the microstructure of the as-synthesised particles. Nd:Y2 O3 powders obtained at 400°C
without organic fuel show agglomeration with a relatively wide size range of 20–100 nm,
as shown in Fig. 4(a). When the mother liquor with NH4 -PAA:YN = 0.2:1 was used, the
agglomeration of powders is slightly alleviated, and the homogeneity and dispersity of the
particles improve. With further increased organic fuel content, as illustrated in the Fig. 4(c),
the powders obtained with NH4 -PAA:YN = 0.5:1 show smaller particle size, narrower size
distribution (20–40 nm), and better dispersity, which indicates that the presence of organic
fuels in the reaction process has favourable influence on the morphology of the end pow-
ders. This observation can be attributed to the dehydration and combustion reactions that
 FERROELECTRICS LETTERS SECTION 23

Figure . TEM images of Nd:Y O powders obtained at  and °C in different mother liquors (a) NH -
PAA:YN = :(°C); (b) NH -PAA:YN = .:(°C); (c) NH -PAA:YN = .:(°C); (d) NH -PAA:YN =
.:(°C).

organic fuels undergo for a short period of time, producing a large amount of gas that effec-
tively relieves agglomeration[15]. Meanwhile, exothermic process during the synthesis reac-
Downloaded by [University of California, San Diego] at 13:59 21 June 2016

tion was observed; hence, an external heat source was not necessary. The powders obtained
by calcining at 800°C are shown in Fig. 4(d). The powders show large particle size, inho-
mogeneous distribution (30–70 nm) and weak agglomeration. Therefore, unreasonably high
calcination temperature negatively affects the microstructure of Nd:Y2 O3 powders.

4. Conclusions
Nanosized Nd:Y2 O3 powders with good dispersity were successfully prepared by combustion
method with ammonium polyacrylate as organic fuel. Cubic Y2 O3 was formed at a relatively
low temperature (300°C), and the crystallinity of powder increased with increased calcina-
tion temperature. However, the unreasonably high calcination temperature was detrimental
to product quality. The dispersity and size distribution of powders increased with increased
organic-fuel dosage. The size distribution of powders obtained at 400°C with NH4 -PAA:YN =
0.5:1 was about 20–40 nm with good dispersity. Therefore, NH4 -PAA was an energy-efficient
organic fuel that can be used to produce Nd:Y2 O3 through solution combustion.

Acknowledgments
This work was supported by the National Natural Science foundation of China through Grant
NO.61201051 and Hubei Science and Technology Innovation Plan (ZDG2014AA017). FI-IR analysis
was conducted at the analytical and testing center of Huazhong University of Science and Technology.

References
[1] Z.Huang,W.Guo,Y.Liu,Q.Huang,F.Tang, and Y.Cao,Synthesis of Nd:Y2 O3 nanopowders leading to
transparent ceramics. Mater Chem Phys.128,44–49 (2011).
[2] Y.Huang,D.Jiang,J.Zhang,Q.Lin, and Z.Huang,Synthesis of Nd:Y2 O3 nanopowders leading to
transparent ceramics. Ceram Int.37,3523–3529 (2011).
[3] X. R.Hou,S. M.Zhou,T. T.Jia,H.Lin, and H.Teng,White light emission in Tm3+ /Er3+ /Yb3+ tri
doped Y2 O3 transparent ceramic. J Alloy Compd.509,2793–2796 (2011).
[4] G. A.Kumar,JianrenLu,Alexander A.Kaminskii,Ken-ichUeda,H.Yagi,Takakimi, and Yanagi-
tani,Spectroscopic and Stimulated Emission Characteristics of Nd3+ in Transparent Y2 O3
Ceramics. IEEE J Quantum Elect.42,643–650 (2006).
[5] L. Q.An,AkihikoIto, and TakashiGoto,Transparent yttria produced by spark plasma sintering at
moderate temperature and pressure profile. J Eur Ceram Soc.32,1035–1040 (2012).
[6] A.Dupont,C.Parent,B.Le Garrec, and J. M.Heintza,Size and morphology control of Y2 O3
nanopowders via a sol–gel route. J Solid State Chem.171,152–160 (2003).
 24 X. ZHANG ET AL.

[7] J.Zhang,S. W.Wang,T. J.Rong, and L. D.Chen,Upconversion Luminescence in Er3+ Doped and
Yb3+ /Er3+ Codoped Yttria Nanocrystalline Powders. J. Am. Ceram. Soc.87,1072–1075 (2004).
[8] W.Li,S.Zhou,H.Lin,H.Teng,N.Liu,Y.Li,X.Hou, and T.Jia,Controlling of Grain Size with Different
Additives in Tm:Y2 O3 Transparent Ceramics. J. Am. Ceram. Soc.93,3819–3822 (2010).
[9] J.Wan,Z.Wang,X.Chen,L.Mu, and Y.Qian,Shape-tailored photoluminescent intensity of red phos-
phor Y2 O3 :Eu3+ . J Cryst Growth.284,538–543 (2005).
[10] P. K.Sharma,M. H.Jilavi,R.Nab, and H.Schmidt,Seeding effect in hydrothermal synthesis of nano-
size yttria. J Mater Sci.17,823–825 (1998).
[11] J.Dhanaraj,R.Jagannathan,T. R. N.Kutty, and C. H.Lu,Photoluminescence Characteristics of
Y2 O3 : Eu3+ Nanophosphors Prepared Using Sol−Gel Thermolysis. J. Phys. Chem. B.105,11098–
11105 (2001).
[12] M.Rekha,K.Laishram,R. K.Gupta,N.Malhan, and A. K.Satsangi,Energy-efficient green synthesis
of Nd:Y2 O3 nanopowder by microwave gel combustion. J Mater Sci.44,4252–4257 (2009).
[13] Z.Qi,C.Shi,W.Zhang,W.Zhang, and T.Hu,Local structure and luminescence of nanocrystalline
Y2 O3 :Eu. Appl Phys Lett.81,2857–2859 (2002).
Downloaded by [University of California, San Diego] at 13:59 21 June 2016

[14] G.Yao,L. B.Su,X. D.Xa,J.Xu,Eu:Y2 O3 nano-phosphor prepared by novel energy-saving solution

combustion method. J Alloy Compd.462,381–385 (2008).
[15] J.McKittrick,L. E.Shea,C. F.Bacalski,E. J.Boszea,The influence of processing parameters on lumi-
nescent oxides produced by combustion synthesis. Displays.19,169–172 (1999).
[16] L.Xu,B.Wei,Z. G.Zhang,Z. L. H.Gao, and Y.Zhang,Synthesis and luminescence of europium doped
yttria nanophosphors via a sucrose-templated combustion method. Nanotechnology.17,4327–
4331 (2006).
[17] Y.Tao,G. W.Zhang,W. P.Zhang, and S. D.Xia,Combustion synthesis and photouiecence of
nanocrstallie Y2 O3 : Eu phsphors. Materials Research Bulletin.32,501–506 (1997).
[18] C. N.Wang,J. B.Zhao,Y.Li,W. P.Zhang, and M.Yin,Influence of dispersant on Y2 O3 : Eu3+ powders
synthesized by combustion method. Journal of rare earths.27,879–885 (2009).